title: Highly fluorous complexes of nickel, palladium and platinum: solubility and catalysis in high pressure CO2.
abstract: A variety of Group 10 metal complexes [MXY(dfppp)], M = Ni, X, Y = Cl, Br, M = Pd, Pt, X, Y = Cl or CH(3), containing the recently reported highly fluorous diphosphine ligand, dfppp, 1,3-bis[di(fluoroponytail)phosphino]propane, {(p-F(13)C(6)C(6)H(4))(2)P}(2)(CH(2))(3) have been synthesised. They have been characterised by NMR, mass spectrometry and microanalysis, with two platinum complexes, [PtCl(2)(dfppp)] and [PtClMe(dfppp)], structurally characterised by single crystal X-ray diffraction studies. The highly fluorous nature of the ligands affords the complexes good supercritical CO(2) solubility as measured by supercritical fluid extraction (SFE), and has allowed for the copolymerisation of CO and ethylene using [PdClMe(dfppp)] as the catalyst precursor and CO(2) as the solvent. Additionally, PtCl(2) complexes of the new ligands dfppb, {(p-F(13)C(6)C(6)H(4))(2)P}(2)(CH(2))(4), and dfpop, {(p-F(13)C(6)C(6)H(4)O)(2)P}(2)(CH(2))(3), have also been prepared and characterised.
authors.affiliation: Chemistry, School of Biomedical, Biomolecular and Chemical Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA, Australia, 6009.
authors.forename: Bradley M
authors.initials: BM
authors.lastname: Berven
authors.forename: George A
authors.initials: GA
authors.lastname: Koutsantonis
authors.forename: Brian W
authors.initials: BW
authors.lastname: Skelton
authors.forename: Robert D
authors.initials: RD
authors.lastname: Trengove
authors.forename: Allan H
authors.initials: AH
authors.lastname: White
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D019216:Metals, Heavy / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry; D010984:Platinum / Q000737:chemistry; D058105:Polymerization; D011312:Pressure; D012995:Solubility
chemical_list: D019216:Metals, Heavy; D009942:Organometallic Compounds; D010720:Phosphines; D002245:Carbon Dioxide; D010984:Platinum; D010165:Palladium; D009532:Nickel